JP2016104488A - Method for treating ammonia-containing waste water - Google Patents
Method for treating ammonia-containing waste water Download PDFInfo
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- JP2016104488A JP2016104488A JP2016040007A JP2016040007A JP2016104488A JP 2016104488 A JP2016104488 A JP 2016104488A JP 2016040007 A JP2016040007 A JP 2016040007A JP 2016040007 A JP2016040007 A JP 2016040007A JP 2016104488 A JP2016104488 A JP 2016104488A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 80
- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 25
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 24
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 24
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 7
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 69
- 230000001590 oxidative effect Effects 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000008155 medical solution Substances 0.000 claims description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 description 25
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229910052801 chlorine Inorganic materials 0.000 description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 20
- 238000000354 decomposition reaction Methods 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910019093 NaOCl Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- -1 ammonium ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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Abstract
Description
本発明はアンモニア含有排水の処理方法に係り、特に、アンモニア含有排水を次亜臭素酸及び／又は次亜臭素酸塩により処理する方法に関する。 The present invention relates to a method for treating ammonia-containing wastewater, and more particularly, to a method for treating ammonia-containing wastewater with hypobromite and / or hypobromite.
製鉄所、製油所、化学工場、メッキ工場、肥料工場などにはアンモニアを多量に含む排水がある。このアンモニアの除去方法としては、生物学的硝化脱窒方法、ストリッピング方法、塩素酸化法（ブレークポイント法（特許文献１））などが知られている。 Steelworks, refineries, chemical factories, plating factories, fertilizer factories, etc. have wastewater containing a large amount of ammonia. As this ammonia removal method, a biological nitrification denitrification method, a stripping method, a chlorine oxidation method (breakpoint method (Patent Document 1)) and the like are known.
生物学的硝化脱窒法は、硝化細菌により窒素ガスに還元する方法である。しかしながら本法における反応は微生物反応であるため、種々の変動要因に対して不安定である、設置面積が広い、汚泥の処理が必要となる等の欠点がある。 The biological nitrification denitrification method is a method of reducing to nitrogen gas by nitrifying bacteria. However, since the reaction in this method is a microbial reaction, there are disadvantages such as being unstable with respect to various fluctuation factors, a large installation area, and requiring treatment of sludge.
ストリッピング法は、アルカリ性下で大量の空気と接触させて、気中放散する方法である。しかしながらこの方法では、アルカリコストがかかると共に、放散させたアンモニアを処理する必要があり、処理コストが高い。 The stripping method is a method of releasing in the air by contacting with a large amount of air under alkaline conditions. However, this method requires an alkali cost, and it is necessary to treat the diffused ammonia, so that the treatment cost is high.
塩素酸化法は、塩素の添加によりアンモニアを結合塩素の一種であるクロラミン経由で窒素ガスに酸化する方法である。この塩素酸化法では、アルカリ条件下において次亜塩素酸とアンモニアが反応し、比較的安定なクロラミンが生成する。 The chlorine oxidation method is a method in which ammonia is oxidized to nitrogen gas via chloramine, which is a kind of combined chlorine, by adding chlorine. In this chlorine oxidation method, hypochlorous acid and ammonia react under alkaline conditions to produce relatively stable chloramine.
ＯＣｌ−＋ＮＨ３→ＮＨ２Ｃｌ＋ＯＨ− …（１）
ＮＨ２Ｃｌ＋ＨＯＣｌ→ＮＨＣｌ２＋Ｈ２Ｏ …（２）
ＮＨＣｌ２＋ＨＯＣｌ→ＮＣｌ３＋Ｈ２Ｏ …（３）
２ＮＨＣｌ２＋Ｈ２Ｏ→Ｎ２＋３Ｈ＋＋３Ｃｌ−＋ＨＯＣｌ …（４）
ＮＨ２Ｃｌ＋ＮＨＣｌ２→Ｎ２＋３ＨＣｌ …（５）
OCl − + NH 3 → NH 2 Cl + OH − (1)
NH 2 Cl + HOCl → NHCl 2 + H 2 O (2)
NHCl 2 + HOCl → NCl 3 + H 2 O (3)
2NHCl 2 + H 2 O → N 2 + 3H + + 3Cl − + HOCl (4)
NH 2 Cl + NHCl 2 → N 2 + 3HCl (5)
アルカリ条件では、上記（５）式の通り、クロラミンが徐々に酸化分解され、窒素と塩酸に分解される。しかしながら、経由物であるクロラミンが比較的安定で、かつ結合塩素であるため、アンモニアが高濃度の時には残留酸化剤濃度が上昇する。また、ＯＣｌ−、ＮＨ２Ｃｌ、ＮＨＣｌ２が高濃度の状態となり、ガスが発生する。また、クロラミンの分解が進まないと、アンモニアの分解が進まない。 Under alkaline conditions, chloramine is gradually oxidized and decomposed into nitrogen and hydrochloric acid as shown in the above formula (5). However, since chloramine, which is a transit, is relatively stable and is bound chlorine, the residual oxidant concentration increases when the ammonia concentration is high. Further, OCl − , NH 2 Cl, and NHCl 2 are in a high concentration state, and gas is generated. Moreover, unless chloramine decomposition proceeds, ammonia decomposition does not proceed.
塩素酸化法では、アンモニアの濃度に対して１０倍程度の塩素が必要であり、かつクロラミンの分解が始まるまでアンモニアの濃度が低下しない。アンモニアが多量の場合はブレークポイントに至るまでに多量のクロラミンが発生し、残留酸化剤が高濃度となり有害なガスを発生する危険性が高くなる。 In the chlorine oxidation method, about 10 times as much chlorine as the ammonia concentration is required, and the ammonia concentration does not decrease until chloramine decomposition begins. In the case of a large amount of ammonia, a large amount of chloramine is generated by the time the break point is reached, and the residual oxidant becomes high in concentration and the risk of generating harmful gases increases.
また、塩素酸化法は、水中のアンモニアの大部分を分解するのには適しているが、アンモニアの部分分解には適さない。アンモニアを含む水を排水する工場では、工場ごとにアンモニアの排水基準を設けている場合が多く、例えば、アンモニウムイオン濃度を所定濃度以下まで下げたいなどのニーズがある。このような場合、従来の塩素酸化法による処理は適していない。 The chlorine oxidation method is suitable for decomposing most of ammonia in water, but not suitable for partial decomposition of ammonia. In factories that drain ammonia-containing water, there are many cases where ammonia drainage standards are set for each factories. For example, there is a need to reduce the ammonium ion concentration to a predetermined concentration or less. In such a case, the treatment by the conventional chlorine oxidation method is not suitable.
本発明は、上記従来の問題点を解決し、高濃度のアンモニア分解時でも有害ガス発生が防止され、またアンモニアの部分分解にも適するアンモニア含有水の処理方法を提供することを目的とする。 An object of the present invention is to solve the above-mentioned conventional problems, and to provide a method for treating ammonia-containing water, which can prevent generation of harmful gas even at the time of high concentration ammonia decomposition and is suitable for partial decomposition of ammonia.
本発明のアンモニア含有排水の処理方法は、アンモニア含有排水に次亜臭素酸及び／又は次亜塩素酸を含む薬液を添加してアンモニアを酸化分解する工程を有するものである。 The method for treating ammonia-containing wastewater of the present invention includes a step of oxidizing and decomposing ammonia by adding a chemical solution containing hypobromite and / or hypochlorous acid to the ammonia-containing wastewater.
本発明の一態様では、薬液は酸化剤成分として、実質的に次亜臭素酸及び／又は次亜臭素酸塩のみを含む。本発明の別の一態様では、薬液は、酸化剤成分として、次亜臭素酸及び／又は次亜臭素酸塩と、次亜塩素酸及び／又は次亜塩素酸塩とを含む。
本発明における「アンモニア」はアンモニウムイオンを含む。
In one embodiment of the present invention, the chemical liquid substantially contains only hypobromite and / or hypobromite as the oxidant component. In another one aspect | mode of this invention, a chemical | medical solution contains hypochlorous acid and / or hypobromite, and hypochlorous acid and / or hypochlorite as an oxidizing agent component.
“Ammonia” in the present invention includes ammonium ions.
本発明のアンモニア含有排水の処理方法では、次亜臭素酸イオンによりアンモニアが次式の反応に従って酸化分解される。 In the method for treating ammonia-containing wastewater of the present invention, ammonia is oxidatively decomposed by hypobromite ions according to the reaction of the following formula.
ＯＢｒ−＋ＮＨ４ ＋→ＮＨ３Ｂｒ＋＋ＯＨ−
２ＮＨ３Ｂｒ＋＋ＯＢｒ−→Ｎ２＋３Ｂｒ−＋Ｈ２Ｏ＋２Ｈ＋
２ＮＨ４ ＋＋３ＯＢｒ−→Ｎ２＋３Ｂｒ−＋３Ｈ２Ｏ＋２Ｈ＋
本発明では、塩素剤を添加しないか又は添加量が少ないので、アンモニア濃度の高いアンモニア含有排水を処理する場合でも、塩素ガスは全く又は殆ど発生しない。
OBr − + NH 4 + → NH 3 Br + + OH −
2NH 3 Br + + OBr − → N 2 + 3Br − + H 2 O + 2H +
2NH 4 + + 3OBr − → N 2 + 3Br − + 3H 2 O + 2H +
In the present invention, since no chlorinating agent is added or the amount added is small, even when treating ammonia-containing wastewater having a high ammonia concentration, no or little chlorine gas is generated.
本発明方法の場合、アルカリ条件ではブロマミン（ブロモアミン）が生成するが、不安定であり、すぐに窒素と臭素に分解される。ブロマミンから窒素への分解が早いために、アンモニアが高濃度でもブロマミンとして高濃度になることはない。このため残留酸化剤濃度も低く、有害ガスの発生も少ない。また、ブロマミンの分解が早く、アンモニアの分解も進みやすい。 In the method of the present invention, bromamine (bromoamine) is produced under alkaline conditions, but it is unstable and immediately decomposes into nitrogen and bromine. Due to the rapid decomposition of bromamine into nitrogen, high concentrations of ammonia do not increase as bromamine. Therefore, the residual oxidant concentration is low and the generation of harmful gases is small. In addition, the decomposition of bromamine is fast and the decomposition of ammonia is easy to proceed.
また、本発明方法では、次亜臭素酸及び／又は次亜臭素酸塩の添加量の増加に伴って、アンモニア濃度が直線的に低下するため、処理水中のアンモニア濃度を目標濃度以下となるように次亜臭素酸及び／又は次亜臭素酸塩の添加量を調整してアンモニアを部分酸化することが容易である。 In the method of the present invention, the ammonia concentration decreases linearly with an increase in the amount of hypobromite and / or hypobromite, so that the ammonia concentration in the treated water is less than the target concentration. In addition, it is easy to partially oxidize ammonia by adjusting the addition amount of hypobromite and / or hypobromite.
以下、本発明についてさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明において、処理対象となるアンモニア含有排水としては、製鉄所排水、めっき工場排水、電子工業排水、石油精製工場排水などのアンモニア含有排水が例示されるが、これに限定されない。 In the present invention, examples of the ammonia-containing wastewater to be treated include ammonia-containing wastewater such as ironworks wastewater, plating factory wastewater, electronic industrial wastewater, and oil refinery factory wastewater, but are not limited thereto.
通常の場合、このようなアンモニア含有排水のアンモニアの濃度は１０ｍｇ／Ｌ以上例えば１０〜１００００ｍｇ／Ｌ程度である。またｐＨは６〜１０程度である。 In normal cases, the ammonia concentration of such ammonia-containing wastewater is 10 mg / L or more, for example, about 10 to 10000 mg / L. Moreover, pH is about 6-10.
アンモニア含有排水は、石炭やコークス由来などの有機物を含有する場合がある。有機物の濃度は、通常、１ｍｇ／Ｌ以上例えば１〜１５００ｍｇ／Ｌ程度である。 The ammonia-containing wastewater may contain organic substances such as coal and coke. The density | concentration of organic substance is 1 mg / L or more normally, for example, about 1-1500 mg / L.
次亜臭素酸及び／又は次亜臭素酸塩が添加されて処理されているときのアンモニア含有排水のｐＨは７〜１２特に８〜１０程度であることが好ましく、必要に応じＮａＯＨ等によってｐＨ調整することが好ましい。 It is preferable that the pH of the ammonia-containing wastewater when the treatment is performed with the addition of hypobromite and / or hypobromite is preferably 7 to 12, particularly about 8 to 10, and adjusted with NaOH or the like as necessary. It is preferable to do.
次亜臭素酸及び／又は次亜臭素酸塩を添加した後のアンモニア含有排水のＯＲＰは４２０ｍＶ以上例えば４２０〜８００ｍＶ特に４２０〜６５０ｍＶ程度が好ましい。 The ORP of the ammonia-containing waste water after adding hypobromite and / or hypobromite is preferably 420 mV or more, for example, 420 to 800 mV, particularly about 420 to 650 mV.
本発明では、このようなアンモニア含有排水に次亜臭素酸及び／又は次亜臭素酸塩を含む薬液を添加してアンモニアを分解する。 In the present invention, a chemical solution containing hypobromite and / or hypobromite is added to such ammonia-containing wastewater to decompose ammonia.
本発明の一態様では、薬液は酸化剤成分として、実質的に次亜臭素酸及び／又は次亜臭素酸塩のみを含む。本発明の別の一態様では、薬液は、酸化剤成分として、次亜臭素酸及び／又は次亜臭素酸塩と、次亜塩素酸及び／又は次亜塩素酸塩とを含む。 In one embodiment of the present invention, the chemical liquid substantially contains only hypobromite and / or hypobromite as the oxidant component. In another one aspect | mode of this invention, a chemical | medical solution contains hypochlorous acid and / or hypobromite, and hypochlorous acid and / or hypochlorite as an oxidizing agent component.
上記の塩としては、ナトリウム塩又はカリウム塩が挙げられるが、特にナトリウム塩が好ましい。 Examples of the salt include sodium salt and potassium salt, and sodium salt is particularly preferable.
次亜臭素酸又は次亜臭素酸塩は、次亜塩素酸又はその塩（好ましくは次亜塩素酸ナトリウム）と臭素及び／又は臭化物好ましくは臭化ナトリウムとを反応させて生成させることが好ましい。次亜塩素酸と臭化ナトリウムとは次式に従って等モルで反応して次亜臭素酸が生成する。 Hypobromite or hypobromite is preferably produced by reacting hypochlorous acid or a salt thereof (preferably sodium hypochlorite) with bromine and / or bromide, preferably sodium bromide. Hypochlorous acid and sodium bromide react in equimolar amounts according to the following formula to form hypobromous acid.
ＨＯＣｌ＋ＮａＢｒ→ＨＯＢｒ＋ ＮａＣｌ
次亜塩素酸ナトリウムと臭化ナトリウムとは次式に従って等モルで反応して次亜臭素酸ナトリウムが生成する。
ＮａＯＣｌ＋ＮａＢｒ→ＮａＯＢｒ＋ＮａＣｌ
なお、臭素及び／又は臭化物と反応させる次亜塩素酸は、塩素を水に溶解させて次亜塩素酸を生成させた塩素溶解水であってもよい。
HOCl + NaBr → HOBr + NaCl
Sodium hypochlorite and sodium bromide react in equimolar amounts according to the following formula to form sodium hypobromite.
NaOCl + NaBr → NaOBr + NaCl
The hypochlorous acid to be reacted with bromine and / or bromide may be chlorine-dissolved water in which chlorine is dissolved in water to produce hypochlorous acid.
アンモニア含有排水に対する次亜臭素酸及び／又は次亜臭素酸塩あるいはさらに次亜塩素酸及び／又は次亜塩素酸塩を含有する液（薬液）の添加量は、原水中のアンモニア濃度に応じて設定すればよい。アンモニア含有排水中のアンモニアの大部分を分解する場合、処理すべきアンモニア量（モル量）の１．０〜１０．０倍特に１．２〜３．０倍（モル量）の酸化剤（次亜臭素酸及び／又は次亜臭素酸塩あるいはさらに次亜塩素酸及び／又は次亜塩素酸塩）をアンモニア含有排水に添加するのが好ましい。また、処理水中の目標アンモニア濃度以下となる酸化剤添加量を予備実験により求めておき、この添加量となるように薬液添加を行うようにしてもよい。 The amount of hypobromite and / or hypobromite or a liquid (chemical solution) containing hypochlorous acid and / or hypochlorite to the ammonia-containing wastewater depends on the ammonia concentration in the raw water. You only have to set it. When decomposing most of the ammonia in the ammonia-containing wastewater, 1.0 to 10.0 times the amount of ammonia to be treated (molar amount), especially 1.2 to 3.0 times (molar amount) oxidizing agent (next) Bromine acid and / or hypobromite or further hypochlorous acid and / or hypochlorite) is preferably added to the ammonia-containing waste water. Further, the amount of oxidant added that is equal to or lower than the target ammonia concentration in the treated water may be obtained by preliminary experiments, and the chemical solution may be added so that this amount is added.
アンモニア含有排水に対して次亜臭素酸及び／又は次亜臭素酸塩と次亜塩素酸及び／又は次亜塩素酸塩とを添加する場合、次亜臭素酸及び／又は次亜臭素酸塩の添加モル量は、次亜塩素酸及び／又は次亜塩素酸塩の添加モル量の０．１〜１．０倍特に０．３〜０．５倍とするのが好ましい。 When adding hypobromite and / or hypobromite and hypochlorous acid and / or hypochlorite to ammonia-containing wastewater, the concentration of hypobromite and / or hypobromite The added molar amount is preferably 0.1 to 1.0 times, more preferably 0.3 to 0.5 times the added molar amount of hypochlorous acid and / or hypochlorite.
アンモニア含有排水の処理は、槽内でバッチ式に行ってもよく、アンモニア含有排水を反応槽に連続的に流入させ、かつ該反応槽から連続的に流出させ、該反応槽にてアンモニア分解反応を行ってもよく、アンモニア含有排水を配管に流し、この配管に塩素源、臭素源及び必要に応じアルカリを添加してライン処理してもよい。 The treatment of the ammonia-containing wastewater may be carried out batchwise in the tank, and the ammonia-containing wastewater is continuously flowed into and out of the reaction tank, and the ammonia decomposition reaction is carried out in the reaction tank. Alternatively, ammonia-containing waste water may be flowed through a pipe, and a chlorine source, a bromine source, and an alkali may be added to the pipe as needed to perform line treatment.
本発明では、アンモニア含有排水の水温を４０℃以上例えば４０〜８０℃特に５０〜７０℃程度とし、これによりアンモニア分解反応速度を大きくしてもよい。加熱コストを抑制するために、水温は８０℃以下、特に７０℃以下とすることが好ましい。 In the present invention, the water temperature of the ammonia-containing waste water may be 40 ° C. or higher, for example, 40 to 80 ° C., particularly about 50 to 70 ° C., thereby increasing the ammonia decomposition reaction rate. In order to suppress the heating cost, the water temperature is preferably 80 ° C. or lower, particularly 70 ° C. or lower.
以下実施例及び比較例について説明する。なお、以下の実施例及び比較例ではアンモニウムイオン濃度分析は、ＪＩＳ Ｋ ０１０２により測定した。全残留塩素濃度と、遊離残留塩素濃度は、ＤＰＤ試薬を用いてハック社製残留塩素計により測定した。結合塩素濃度は全残留塩素濃度から遊離残留塩素濃度を減算して求めた。 Examples and comparative examples will be described below. In the following Examples and Comparative Examples, ammonium ion concentration analysis was measured according to JIS K 0102. The total residual chlorine concentration and the free residual chlorine concentration were measured with a residual chlorine meter manufactured by Hack using a DPD reagent. The combined chlorine concentration was determined by subtracting the free residual chlorine concentration from the total residual chlorine concentration.
塩素ガス発生の有無は、理研計器株式会社製塩素ガスモニター（０．５ｐｐｍ以上で警報発生）により判定した。 The presence or absence of generation of chlorine gas was determined by a chlorine gas monitor manufactured by Riken Keiki Co., Ltd. (alarm generated at 0.5 ppm or more).
［実施例１〜６（次亜臭素酸ナトリウム含有液による処理）］
試験水として次の水質の製鉄所排水を用いた。
[Examples 1 to 6 (treatment with sodium hypobromite-containing solution)]
The following water quality steelworks effluent was used as test water.
ｐＨ：８．２
アンモニウムイオン濃度：４１０ｍｇ／Ｌ（２２．７ｍ ｍｏｌ／Ｌ）
ＴＯＣ：２１ｍｇ／Ｌ
ＯＲＰ：２３６ｍＶ
pH: 8.2
Ammonium ion concentration: 410 mg / L (22.7 mmol / L)
TOC: 21 mg / L
ORP: 236 mV
薬液としての次亜臭素酸ナトリウム含有液としては、４０ｗｔ％濃度の臭化ナトリウム溶液と１２ｗｔ％濃度の次亜塩素酸ナトリウム溶液とをＮａＢｒ：ＮａＯＣｌ＝１：１（モル比）となる比率にて混合し、次亜臭素酸ナトリウムを生成させた液を用いた。 As a liquid containing sodium hypobromite as a chemical solution, a sodium bromide solution with a concentration of 40 wt% and a sodium hypochlorite solution with a concentration of 12 wt% are in a ratio of NaBr: NaOCl = 1: 1 (molar ratio). The liquid which mixed and produced | generated sodium hypobromite was used.
試験水１０００ｍＬをガラス製容器に収容し、水温を５０℃に保ち、ＮａＯＨによりｐＨ９．６とした後、上記の次亜臭素酸ナトリウム水溶液を添加した。反応時間は５ｍｉｎとした。 1000 mL of test water was placed in a glass container, the water temperature was kept at 50 ° C., and the pH was adjusted to 9.6 with NaOH, and then the above sodium hypobromite aqueous solution was added. The reaction time was 5 min.
次亜臭素酸ナトリウム添加量と、上記反応時間経過後の残留塩素濃度、ＯＲＰ、アンモニウムイオン濃度及びアンモニウムイオン分解率を表１に示す。 Table 1 shows the amount of sodium hypobromite added and the residual chlorine concentration, ORP, ammonium ion concentration, and ammonium ion decomposition rate after the reaction time.
［比較例１〜７］
次亜臭素酸ナトリウム含有液の代わりに次亜塩素酸ナトリウム（１２ｗｔ％水溶液）を用い、表１に示す添加量にて添加したこと以外は実施例１〜６と同様にして同一の試験水を処理した。結果を表１に示す。なお、実施例１〜６と比較例１〜６とでは、次亜臭素酸ナトリウムと次亜塩素酸ナトリウムの添加量（モル量）が同一である。
[Comparative Examples 1 to 7]
The same test water was used in the same manner as in Examples 1 to 6 except that sodium hypochlorite (12 wt% aqueous solution) was used instead of the sodium hypobromite-containing solution and the addition amount shown in Table 1 was added. Processed. The results are shown in Table 1. In addition, in Examples 1-6 and Comparative Examples 1-6, the addition amount (molar amount) of sodium hypobromite and sodium hypochlorite is the same.
＜考察＞
表１の通り、次亜臭素酸ナトリウムを用いた実施例１〜６によると、次亜塩素酸ナトリウムを用いた比較例１〜７に比べてアンモニアが十分に分解される。また、実施例１〜６では塩素ガスも発生しない。
<Discussion>
As shown in Table 1, according to Examples 1 to 6 using sodium hypobromite, ammonia is sufficiently decomposed as compared with Comparative Examples 1 to 7 using sodium hypochlorite. In Examples 1 to 6, no chlorine gas is generated.
なお、次亜臭素酸ナトリウム又は次亜塩素酸ナトリウムの添加量（ｍ ｍｏｌ／Ｌ）と処理水中の残留ＮＨ４ ＋濃度との関係を図１に示す。 In addition, the relationship between the addition amount (mmol / L) of sodium hypobromite or sodium hypochlorite and the residual NH 4 + concentration in the treated water is shown in FIG.
図１の通り、次亜臭素酸ナトリウムの場合は、ＮＨ４ ＋濃度は次亜臭素酸ナトリウムの添加量に比例して直線的に低下している。これに対し、次亜塩素酸ナトリウムの場合は、添加量が約２０ｍ ｍｏｌ／Ｌよりも多くなると、ＮＨ４ ＋濃度が急激に低下していることが分かる。このことから、次亜臭素酸ナトリウムを添加してアンモニア分解を行う場合、添加量に比例して残留アンモニア濃度が直線的に減少するので、目標とするアンモニア濃度となるように薬注量を制御することが容易であることが認められた。 As shown in FIG. 1, in the case of sodium hypobromite, the NH 4 + concentration linearly decreases in proportion to the amount of sodium hypobromite added. On the other hand, in the case of sodium hypochlorite, it can be seen that the NH 4 + concentration rapidly decreases when the amount added is greater than about 20 mmol / L. Therefore, when ammonia decomposition is performed with sodium hypobromite added, the residual ammonia concentration decreases linearly in proportion to the amount added, so the dosage is controlled to achieve the target ammonia concentration. It was found to be easy to do.
［実施例７〜２１（次亜臭素酸ナトリウム及び次亜塩素酸ナトリウムによる処理）］
試験水として次の水質の製鉄所排水を用いた。
[Examples 7 to 21 (treatment with sodium hypobromite and sodium hypochlorite)]
The following water quality steelworks effluent was used as test water.
ｐＨ：８．３
アンモニウムイオン濃度：５３２ｍｇ／Ｌ（２９．５ｍ ｍｏｌ／Ｌ）
ＴＯＣ：２２ｍｇ／Ｌ
ＯＲＰ：９０ｍＶ
pH: 8.3
Ammonium ion concentration: 532 mg / L (29.5 mmol / L)
TOC: 22mg / L
ORP: 90mV
次亜臭素酸ナトリウム及び次亜塩素酸ナトリウム含有液としては、４０ｗｔ％濃度の臭化ナトリウム溶液と１２ｗｔ％濃度の次亜塩素酸ナトリウム水溶液とを表２の重量比にて混合して次亜臭素酸ナトリウムを生成させた液を用いた。 As the sodium hypobromite and sodium hypochlorite-containing liquid, a sodium bromide solution having a concentration of 40 wt% and a sodium hypochlorite aqueous solution having a concentration of 12 wt% were mixed at a weight ratio shown in Table 2 to prepare hypobromine. The liquid in which sodium acid was produced was used.
試験水１０００ｍＬをガラス製容器に収容し、水温を５０℃に保ち、ＮａＯＨによりｐＨ９．６とした後、次亜臭素酸ナトリウム水溶液を添加した。反応時間は５ｍｉｎとした。 1000 mL of test water was placed in a glass container, the water temperature was kept at 50 ° C., and the pH was adjusted to 9.6 with NaOH, and then an aqueous sodium hypobromite solution was added. The reaction time was 5 min.
薬剤添加量（ただし試験水に対するＮａＢｒ及びＮａＯＣｌ添加率に換算）と、上記反応時間経過後の残留塩素濃度、アンモニウムイオン濃度及びアンモニウムイオン分解率を表２に示す。 Table 2 shows the amounts of chemicals added (however, converted to NaBr and NaOCl addition rates with respect to the test water), residual chlorine concentration, ammonium ion concentration and ammonium ion decomposition rate after the reaction time.
［比較例８〜１０］
次亜臭素酸ナトリウム含有液を添加せず、次亜塩素酸ナトリウム（１２ｗｔ％水溶液）のみを表２に示す添加量にて添加したこと以外は実施例７〜２１と同様にして同一の試験水を処理した。結果を表２に示す。
[Comparative Examples 8 to 10]
The same test water as in Examples 7 to 21 except that no sodium hypobromite-containing liquid was added and only sodium hypochlorite (12 wt% aqueous solution) was added in the addition amount shown in Table 2. Processed. The results are shown in Table 2.
＜考察＞
表２の通り、次亜臭素酸ナトリウム及び次亜塩素酸ナトリウム含有液を添加した実施例７〜２１によると、次亜塩素酸ナトリウムのみを添加した比較例８〜１０に比べて残留塩素が少なく、またアンモニアが十分に分解される。即ち、次亜臭素酸ナトリウム及び次亜塩素酸ナトリウム含有液を添加すると残留酸化剤濃度の上昇が少なくなる。特に、Ｂｒ比が３０％以上の実施例では、残留酸化剤濃度の上昇が少なく、塩素ガスの発生がない。また、Ｂｒ比が１０％以上では、ＮＨ４ ＋濃度は直線的に減少する。一方、比較例では、初期の残留酸化剤濃度の上昇が高く、塩素ガスの発生がある。また、ＮＨ４ ＋の分解も直線的ではなく、ＮＨ４ ＋に対するＮａＯＣｌの割合が少ない場合のＮＨ４ ＋の分解率は低い。
<Discussion>
As shown in Table 2, according to Examples 7 to 21 in which sodium hypobromite and sodium hypochlorite-containing liquid were added, the residual chlorine was less than in Comparative Examples 8 to 10 in which only sodium hypochlorite was added. In addition, ammonia is sufficiently decomposed. That is, when the sodium hypobromite and sodium hypochlorite containing liquid is added, the increase in residual oxidant concentration is reduced. In particular, in Examples where the Br ratio is 30% or more, the residual oxidant concentration is little increased and no chlorine gas is generated. When the Br ratio is 10% or more, the NH 4 + concentration decreases linearly. On the other hand, in the comparative example, the initial increase in residual oxidant concentration is high, and chlorine gas is generated. Further, the decomposition of NH 4 + is not linear, and the decomposition rate of NH 4 + is low when the ratio of NaOCl to NH 4 + is small.
本発明のアンモニア含有排水の処理方法は、アンモニア含有排水に臭化ナトリウム水溶液と次亜塩素酸ナトリウム水溶液とを混合して次亜臭素酸ナトリウムを生成させた薬液を添加してアンモニアを酸化分解する工程を有するものである。 In the method for treating ammonia-containing wastewater of the present invention, the ammonia-containing wastewater is mixed with an aqueous solution of sodium bromide and an aqueous solution of sodium hypochlorite to add a chemical solution that forms sodium hypobromite to oxidatively decompose and decompose ammonia. It has a process.
本発明の一態様では、薬液は酸化剤成分として、実質的に次亜臭素酸ナトリウムのみを含む。本発明の別の一態様では、薬液は、酸化剤成分として、次亜臭素酸ナトリウムと、次亜塩素酸ナトリウムとを含む。
本発明における「アンモニア」はアンモニウムイオンを含む。
In one aspect of the present invention, the chemical solution as the oxidizing agent component, substantially comprising sodium hypobromite only. In another aspect of the present invention, drug solution, as the oxidizing agent component comprises sodium hypobromite, and sodium hypochlorite.
“Ammonia” in the present invention includes ammonium ions.
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